1. Field of the Invention
This invention relates to a process for the vapor phase nitration of aromatic compounds. More particularly, this invention relates to a process for the vapor phase nitration of aromatic compounds in the presence of a nitration promoting catalyst which comprises the adduct of:
(a) an alumina-silica-metal oxide combination represented by the formula: EQU (Al.sub.2 O.sub.3).sub.a (SiO.sub.2).sub.b (M.sub.2/n O).sub.c
wherein M is a metal cation selected from the group consisting of the lanthanides or rare earths, Groups 1b, 2b, 5b, 6b, 7b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and a, b, and c represent weight percent of the Al.sub.2 O.sub.3, SiO.sub.2, and M.sub.2/n O components, respectively, in the alumina-silica-metal oxide combination, with a being 0 to 100, b being 0 to 100, and c being 0 to 50, and n represents an integer from 1 to 7 of the valence of the metal cation, with the proviso that the sum of (a+b) must be greater than 0, and
(b) a catalytically effective amount of sulfur trioxide.
Nitroaromatic compounds find use as solvents, explosives, dyes, perfumes, and analytical reagents, and are important as intermediates in organic synthesis. As an example, nitroaromatic compounds are convertible by reduction into primary amines, which, in turn, are valuable intermediates in the synthesis of dyes, pharmaceuticals, photographic developers, antioxidants, and gum inhibitors.
2. Description of the Prior Art
Nitroaromatic compounds are currently produced primarily via liquid phase reactions employing mixed acids. A sulfuric acid/nitric acid mixture is the most commonly employed industrial nitrating agent. Other mixed acids for nitration of aromatic compounds are acetic acid/nitric acid mixtures as described, for example, in U.S. Pat. No. 3,180,900. In U.S. Pat. No. 3,928,476, the latter type nitration is conducted over silica-alumina or alumina supports. A sulfonic acid/nitric acid mixture is disclosed as a nitrating agent for the nitration of halobenzenes in U.S. Pat. No. 3,077,502. Reportedly, the sulfonic acid causes a para directive effect, the effect of which is to increase the para-to-ortho isomer distribution above the usual ratio of 1.7.
Vapor phase nitration of aromatic compounds is also known in the art. The vapor phase nitration of benzene and toluene at temperatures ranging from about 275.degree. C. to about 310.degree. C. is described in McKee and Wilhelm, Industrial and Engineering Chemistry, 28(6), 662-667 (1936) and U.S. Pat. No. 2,109,873. McKee and Wilhelm catalyzed their reaction with silica gel, with best results being reported by the use of 14 mesh material. Bauxite and alumina were reported to be ineffective as catalysts in the vapor phase nitration of benzene. More recently, U.S. Pat. No. 4,107,220 described the vapor phase nitration of chlorobenzene in the presence of molecular sieve catalysts having a pore size varying from about 5 A to about 10 A as a means for controlling the para-to-ortho isomer distribution of nitrochlorobenzene. A suitable temperature range was reported to be from about 190.degree. to about 290.degree. C.
Although these prior art processes generally provide the desired product, the choice of available catalysts is severely limited. In addition, the commercial utility of a catalytic process is highly dependent upon the cost of the catalyst employed, the conversion of the reactant(s), and the yield of the desired product(s). In many cases, a reduction in the cost of the catalyst system employed in a given process on the order of a few cents per pound or a small percent increase in the yield of the desired product represents a tremendous commercial economical savings. Thus, the discovery that the vapor phase nitration reaction of the present invention can be carried out in a very efficient manner with high aromatic compound conversion and high nitroaromatic compound selectivity is believed to be a decided advance in the art.